Nitrosation of Lignosulfonates under Solid-Phase Catalysis Conditions

Abstract

Lignosulfonates are the most common commercial lignin-based product due to their unique properties. Various methods are known for modifying lignosulfonates and lignosulfonic acids. This article presents the results of the development of a new approach to the production of nitrosated lignosulfonic acids. The method is based on a reaction catalyzed by cation exchange resins in the H-form: KU-2-8 cation exchanger and wofatite. The influence of reagent consumption and reaction duration on the course of nitrosation has been studied. The dynamics of the proposed nitrosation practically coincides with the dynamics of a similar reaction using sulfuric acid by the known method. The optimal consumption of sodium nitrite equals 15 %, and the optimal consumption of cation exchanger equals 100 % by weight of lignosulfonates. During the nitrosation of lignosulfonates, significant changes in the electronic spectra occur in the region of 280...500 nm. Two overlapping absorption bands appear with maxima at 300 and 330 nm, as well as an intense absorption band at 430 nm, due to nitroso groups conjugated with the aromatic nuclei of phenylpropane units. To analyze the ionization spectra, they have been deconvoluted. The resulting spectra are well approximated by 5 Gaussians with an error of no more than 5 %. Two options for carrying out the nitrosation reaction of lignosulfonates have been proposed: under static and dynamic conditions. It has been established that under dynamic conditions, nitroso derivatives of lignosulfonic acids are formed that do not contain metal cations, and the pH of the resulting solutions does not exceed 1.4. The elemental compositions of the isolated initial and nitrosated lignosulfonic acids have been determined. The nitrogen content of lignosulfonic acids has increased from 0.32 (initial) to 2.17 % (nitrosated). In addition, under dynamic conditions, an additional stage of separating the cation exchanger from the reaction medium by filtration is not required. New bands have appeared in the IR spectrum of nitrosated lignosulfonic acids: at 1540 cm–1, which is due to the presence of nitroso groups, and a wide absorption band at 1700...1715 cm–1, which can be caused by vibrations of the carboxyl group or the quinone monooxime tautomeric form of the guaiacyl structures of lignosulfonic acids.

Keywords

• lignin
• lignosulfonates
• lignosulfonic acids
• modification
• nitrosation
• solid-phase catalysis
• spectrophotometry
• nitrosolignosulfonic acids